Lubricating compositions



LUBRICATING COMPOSITIONS Samuel K. Talley, Berkeley, Frederick M. Fowkes,

Grinda, and Alfredo G. Cattaneo, Berkeley, Calif., assignors to Shell Development Company, Emeryville, Caiii, a corporation of Delaware N0 Drawing. Application April 14, 1953, Serial NO. 348,806

15 Claims. (Cl. 25233.4)

necessary for eflective operation of engines, such as internal combustion engines, particularly when they are operating under cold temperature conditions such as 10 F. or lower. Starting and etficient engine lubrication under cold temperature conditions is even unsatisfactory when lubricating oils having an SAE viscosity of 10 are used alone or even as mixtures thereof with kerosene. Even then, artificial starting means are frequently resorted to, such as electric block heaters, booster batteries, and the like. The use of low viscosity oils for the purpose under such low temperature conditions results in high oil consumption and corrosion.

Various means have been investigated to reduce oil consumption. Mechanical modification of engines to meet cold temperature requirement is costly and has been found to be ineffective. Use of viscosity index improvers and numerous other types of oil additives have also failed to solve this problem.

It is an object of this invention to produce a new and improved cold temperature lubricant. It is also an object of this invention to produce a good cold starting lubricant. Another object of this invention is to reduce oil consumption of low viscosity oils. Still another object of this invention is to provide a novel low viscosity lubricant which is resistant to breakdown and oil consumption. Still another object of this invention is to produce a low viscosity lubricant having a carryover or persistence effect. Other objects will be apparent hereinafter.

It has now been found that oil consumption of light lubricating oil stocks, such as SAE 5W oils, can be reduced by at least 25% and even above 75% at elevated engine operating temperatures by addition to such oils of a minor amount of a perhalo compound wherein the halo atoms have an atomic number of 9 to 17 of which preferred are the perfluoro-organic acid and derivatives thereof, such as acid halides, esters, salts, amides and imides thereof.

Additives of this invention can be prepared by any suitable means such as described in U. S. Patents 2,606,206, 2,567,011, 2,583,415, 2,514,473, and 2,407,315, and in Ind. and Eng. Chem., vol. 43, No. 10, 2332 (1951). Specific compounds which are particularly suitable as oil consumption inhibitors as well as mixtures thereof include: perfluoroacetic acid, perfluoropropionic acid, perfluorobutyric acid, perfluorovaleric acid, perfluorocaproic acid, perfluoroheptanoic acid, perfluorocaprylic acid, perfiuorocapric acid, perfluoromyristic acid, perfluorocyclohexane carboxylic acid, fl-perfluorocyclohexaneacetic acid, perfluorosebacic acid, perfluorosuccinic acid, per fluorobutyryl fluoride, perfluorocapryl fluoride, perfluorocyclohexyl fluoride, perfluoropropionyl chloride, perfluorocapryl chloride; perfluorobutyryl amide, perfluorocapryl amide, perfluorocyclohexaneformamide, u-dichlo- Col Patented Aug. 9, 1955 ro-B-di-fluorochloropropionic acid, ot-dichloro-fl-di-fluorochloropropionamide, perfiuorosebacic acid monoamide, perfluorosuccinirnide, etc.

The perhalo compounds of this invention are suitably used in amounts varying from 0.01 to 5%, and preferably from about 0.1 to 1% by weight of the oil composition.

The perhalo-compounds are compatible with various conventional lubricating oil additives, which can be incorporated in the composition, such as blooming agents, pour-point depressors, detergent viscosity improvers, antifoaming agents, and the like. Among the specific additives for lubricating purposes which can be used are oilsoluble detergents which include oil-soluble salts of various bases with detergent-forming acids. Such bases include metal-containing as well as organic bases. Suitable metallic bases include those of the alkali metals and of polyvalent metals such as Ca, Mg, Cu, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include various nitrogen bases such as primary, secondary, tertiary amines and quaternary ammonium compounds, e. g., benzyl trimethyl ammonium hydroxide.

Representative examples of suitable detergent-forming acids are the fatty acids of say, 10 to 30 carbon atoms, tall-oil acids, rosin acids, wool-fat acids, paraflin-wax acids (produced by oxidation of paraflin wax), chlorinated fatty acids, aromatic hydroxy fatty acids, paraffinwax alkylated benzoic acids, various alkyl salicylic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols such as di-(alkylphenol) sulfides and disulfides, methylene bis-alkyl phenols; sulfonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or high-boiling petroleum oils with sulfuric acid; sulfuric acid monoesters; esters of acids of phosphorus, arsenic and antimony, including the corresponding thiophosphoric and thioarsonic acids and the like.

Illustrative specific detergents which are especially effective in combination with the perfiuorocompounds in mineral lubricating oils are: oil-soluble alkaline earth metal petroleum sulfonates, particularly the calcium and barium sulfonates, including normal and basic salts; alkaline earth metal (particularly calcium and barium) alkylphenates, including simple phenates (calcium cetyl phenate) and dior poly-phenates (barium salt of di- (octylphenol) sulfide, calcium salt of polyoctylphenolpolymethylene such as obtained by the condensation of octylphenol and an aldehyde such as formaldehyde to form products such as penta(octylhydroxyphenylene) tetramethylene, etc.; alkaline earth metal alkylsalicylates such as calcium cetylsalicylate, calcium C14 1s-alkylsalicylate; divalent metal salts of Group II have metals with phosphorus acid partial esters, e. g., zinc dicyclohexyl dithiophosphate and barium di-Z-ethylhexylphosphate; and divalent metal salts of Group II have metals with carbamic and thiocarbamic acids, e. g., zinc dibutyl dithiocarbamate, and calcium dicyclohexyl dithiocarbamate. The metal containing detergents are advantageously used in an amount of from about 0.025% to about 0.2% by weight, determined as sulfate ash of the metal content.

Corrosion inhibitors or anti-rusting compounds may also be present, such as alkyl or alkenyl dicarboxylic acids of 16 or more carbon atoms (octadecylsuccinic acid); alkali metal and alkaline earth metal salts of sulfonic acids and of fatty acids, organic compounds containing an acidic radical in close proximity to a nitrile, nitro, or nitroso group (e. g., alphacyanostearic acid), glycidyl phenyl ether, wax disulfide, etc.

Additional ingredients may comprise oil-soluble urea or thiourea derivatives, e. g., urethanes, allophanates, carbazides, carbazones, etc., alkylene polymers such as polyisobutylene, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high-molecular-weight oil-soluble compounds.

Depending upon the additional additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with the primary additive of this invention.

Base oils with which additives of this invention are combined include light lubricating oil having a Saybolt Universal viscosity at 210 P. not in excess of around 45 seconds and include natural and synthetic oils such as esters of polycarboxylic acid (Z-ethylhexylsebacate), Ucon fluids (polyalkylene oxides) organic silicone fluids, etc., as well as mixtures thereof. A typical oil of this type is an SAE SW petroleum motor oil having the following properties:

Flash point, F 385 Pour point, F 10 Viscosity, SVS at 210 F 39.7 Viscosity index 95 Additives of this invention are ineffective in reducing oil consumption for high viscosity oils such as SAE 20, 30 and higher viscosity oils. Their effectiveness is only found in oils of low viscosity as identified above.

The following examples are illustrative of compositions of this invention, wherein the SAE W motor designates an oil having the characteristics given above:

Example 1: Per cent weight Perfluorocaprylamide 0.2 SAE 5W motor oil Balance Example 2:

Perfluorocaprylic acid 0.2 SAE 5W motor oil Balance Example 3:

Perfiuorosebacic acid 0.1 SAE 5W motor oil Balance Example 4:

Perfluorocaprylamide 0.2 Ca-petroleum mahogany sulfonate 0.4 SA SAE 5W motor oil Balance Example 5:

Perfluorocaprylamide 0.2

Ca salt of octyl phenol-formaldehyde condensation product containing an average of about 5 phenol units per molecule 0.3 SA SAE 5W motor oil Balance Example 6:

Perfluorocaprylic acid 0.2 Cat-petroleum mahogany sulfonate 0.1 SA Ca salt of octyl phenol-formaldehyde condensation product (MW 9801500) 0.3 SA SAE 5W motor oil Balance Example 7:

a-Dichloro-ddifiuorochloropropi acid 0.1 SAE 5W motor oil Balance Example 8:

Perfluorocaprylamide 0.3 Ucon Fluid (carbon and carbide cup) (SVS at 210 Pa, 41 sec.) Balance Example 9:

Perchloroacetamide 0.1 Perfiuoromyristie acid 0.2 SAE 5W motor oil Balance Example 10:

Acetamide 0.1 Perfiuorosuccimide 0.2 SAE 5W motor oil Balance Example 11:

Perfiuorocaprylamide 0.3 Ca-petroleum mahogany sulfonate 0.1 SA

Ca salt of octyl phenol-formaldehyde condensation product (MW 9801500) 0.3 SA SAE 5W motor oil Balance TABLE 1 Reduction in oil consumption, per cent a 5,000 Mile Field Test Chevrolet Engme Composition E (ORG 55 Hand' Ford nib th book) Car Car Example 1 67 60 60 60 Example 2 50 50 Example 4.. 70 6O 6O Example a 75 70 7o Compos t on X none none none none Composition Y none none none none 8 Percent reduction in oil consumption calculated on base oil (SAE 5W) b Composition X=SAE 5W motor oil+cornmercial VI improver in an amount sufficient to increase the viscosity of the oil to SAE 10W.

0 Composition Y=SAE 30 motor oil+0.2% perfiuorocaprylamide.

In another test a CRC L-4 engine was run on lubricant identified as Example 2 and around 60% reduction in oil consumption was noted. The oil was removed and the engine operated with a straight SAE 5W oil. A reduction of around 25% in oil consumption was noted demonstrating the carryover eiTect of compositions of this invention.

Compositions of this invention, in addition to effectively reducing oil consumption, inhibit wear, corrosion, sludge and lacquer formation. Lubricants of this invention also are particularly advantageous during starting and particularly eliminate the necessity of engine warm-up.

We claim as our invention:

1. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 F. not in excess of 45 seconds and between about 0.01% and about 5% by weight, of a perfluoro-organic compound selected from the group consisting of perfiuoro-organic acids, and amides thereof, said compound containing between 2 and 14 carbon atoms per molecule.

2. A lubricating composition comprising a major amount of a low viscosity petroleum oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and between about 0.01% and about 5% by weight, of a perfiuoroaliphatic acid, said acid contain ing between 2 and 14 carbon atoms per molecule.

3. A lubricating composition comprising a major amount of a low viscosity petroleum oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and between about 0.01% and about 5% by weight, of a perfiuoroamide having between 2 and 14 carbon atoms per molecule.

4. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and from 0.1% to 1% by weight of perfluorocaprylic acid.

5. A lubricating composition comprising a major amount of alow viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and from 0.1% to 1% by weight of perfiuorocaprylamide.

6. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and from 0.1% to 1% by Weight of perfluorocaprylic acid and from 0.01% to 2% by weight of a detergent.

7. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and from 0.1% to 1% by weight of perfluorocaprylamide and from 0.01% to 2% by weight of an anti-wear agent.

8. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 F. not in excess of 45 seconds and from 0.1% to 1% by weight of perfiuorocaprylic acid and from 0.01% to 2% by Weight of an oil-soluble sulfonate.

9. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and from 0.1% to 1% by weight of perfluorocaprylamide and from 0.01% to 2% by weight of an oil-soluble metal phenate.

10. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 F. not in excess of 45 seconds and from 0.1% to 1% by weight of perfluorocaprylic acid and from 0.01% to 2% by weight each of an oil-soluble metal sulfonate and an oil-soluble metal phenate.

11. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and from 0.1% to 1% by weight of a perfluorocaprylamide and from 0.01% to 2% by weight each of a metal sulfonate and a metal phenate.

12. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and from 0.1% to 1% by weight of a perfiuorocaprylic acid and from 0.1% to 0.5% by Weight each of an oilsoluble calcium petroleum sulfonate and an oil-soluble calcium salt of alkyl phenol-formaldehyde condensation product.

13. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of seconds and from 0.1% to 1% by weight of a perfiuorocaprylamide and from 0.1% to 0.5% by weight each of oil-soluble calcium petroleum sulfonate and oil-soluble calcium salt of alkyl phenol-formaldehyde condensation product.

14. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 P. not in excess of 45 seconds and containing about 0.2% perfluorocaprylamide and about 0.4% calcium petroleum sulfonate.

15. A lubricating composition comprising a major amount of a low viscosity oil having a Saybolt Universal viscosity at 210 F. not in excess of 45 seconds and containing about 0.2% perfluorocaprylic acid, 0.1% calcium petroleum sulfonate and 0.3% calcium salt of octyl phenol-formaldehyde condensation product.

References Cited in the file of this patent UNITED STATES PATENTS Re. 23,229 Grifiin May 9, 1950 2,411,159 Hanford Nov. 19, 1946 2,456,176 Cramer Dec. 14, 1948 2,567,011 Diesslin Sept. 4, 1951 2,606,212 McBee Aug. 5, 1952 2,616,927 Kauck Nov. 4, 1952 2,680,717 Little June 8, 1954 

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF A LOW VISCOSITY OIL HAVING A SAYBOLT UNIVERSAL VISCOSITY AT 210* F. NOT IN EXCESS OF 45 SECONDS AND BETWEEN ABOUT 0.01% AND ABOUT 5% BY WEIGHT, OF A PERFLUORO-ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF PERFLUORO-ORGANIC ACIDS, AND AMIDES THEREOF, SAID COMPOUND CONTAINING BETWEEN 2 AND 14 CARBON ATOMS PER MOLECULE. 